WO2011120336A1 - 乙烯齐聚催化剂组合物和齐聚方法 - Google Patents

乙烯齐聚催化剂组合物和齐聚方法 Download PDF

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WO2011120336A1
WO2011120336A1 PCT/CN2011/000550 CN2011000550W WO2011120336A1 WO 2011120336 A1 WO2011120336 A1 WO 2011120336A1 CN 2011000550 W CN2011000550 W CN 2011000550W WO 2011120336 A1 WO2011120336 A1 WO 2011120336A1
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cocatalyst
oligomerization
main catalyst
ethylene
ipr
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PCT/CN2011/000550
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English (en)
French (fr)
Inventor
郑明芳
李维真
王怀杰
刘珺
张海英
周钰
栗同林
赵岚
王吉龙
吴红飞
朴玉玲
隋军龙
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中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
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Priority claimed from CN2010101381271A external-priority patent/CN102206127A/zh
Priority claimed from CN201010500316.9A external-priority patent/CN102432414B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to US13/637,976 priority Critical patent/US20130018214A1/en
Priority to KR1020127028616A priority patent/KR101760821B1/ko
Priority to GB1219506.1A priority patent/GB2494555B/en
Priority to JP2013501602A priority patent/JP5909224B2/ja
Priority to RU2012146245/04A priority patent/RU2571829C2/ru
Publication of WO2011120336A1 publication Critical patent/WO2011120336A1/zh
Priority to ZA2012/08192A priority patent/ZA201208192B/en

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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
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    • C08F4/00—Polymerisation catalysts
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    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7039—Tridentate ligand
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Definitions

  • the present invention relates to the field of ethylene oligomerization, and in particular to a catalyst composition of 2-aminoimido-1,10-phenanthroline iron (II), cobalt (II) or nickel (II) and triethylaluminum.
  • the invention also relates to an ethylene oligomerization process using the above composition. Background technique
  • Linear ⁇ -olefins have a wide range of applications in the fields of ethylene comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricants and oil additives.
  • ethylene comonomers comonomers
  • surfactant synthesis intermediates plasticizer alcohols
  • synthetic lubricants synthetic lubricants
  • oil additives oil additives.
  • the catalysts used in the ethylene oligomerization process are mainly nickel, chromium, zirconium and aluminum.
  • Brookhart Group Brookhart, M et al., J. Am. Chem. Soc., 1998, 120, 7143-7144).
  • Patent CN1850339A of the Institute of Chemistry, Chinese Academy of Sciences reports a catalyst for ethylene oligomerization and polymerization, which is 2-imido-1,10-phenanthroline coordinated Fe 2+ , Co 2+ and Ni 2+ chloride, under the action of cocatalyst fluorenyl aluminoxane, the catalyst as a main catalyst has good ethylene oligomerization and polymerization catalytic properties, wherein the iron complex exhibits high oligomerization and polymerization activity for ethylene.
  • the oligomerization activity is the highest; and the oligomerization and polymerization activity increase with the increase of pressure; the oligomerization products include C 4 , C 6 , C 8 , C 10 , C 12 , C 14 , C 16 , C 18 , C 20 , C 22 , etc.; the polymer is a low molecular weight polyolefin and a waxy polyolefin.
  • This patent also discloses triethyl aluminum as a cocatalyst, chlorinated [2-acetyl-1,10-phenanthroline (2,6-diethylaniline)] iron (ruthenium) as the main catalyst, Al
  • the /Fe ratio is 500
  • the reaction temperature is 40 ° C
  • the reaction time is lh
  • the polymerization pressure is IMP
  • the oligomerization activity is 2.71 ⁇ 10 5
  • the patent also discloses triisobutyl aluminum and diethyl aluminum chloride.
  • the amount of high cocatalyst Al/Fe ratio is 500
  • the oligomerization activity is also low.
  • an ethylene oligomerization catalyst composition comprising 2-imino-1,10-phenanthroline iron (II) and cobalt (II) represented by the following formula (I) Or a nickel (II) procatalyst and a triethylaluminum cocatalyst, wherein the molar ratio of the metal aluminum in the cocatalyst to the central metal in the procatalyst is from 30 to less than 200:
  • M is a central metal selected from the group consisting of Fe 2+ , Co 2+ and Ni 2+ ;
  • R ⁇ Rs are each independently selected from the group consisting of hydrogen, ⁇ C 6 alkyl, halogen, d ⁇ C 6 alkoxy And nitro.
  • Ci- C6 alkyl means a saturated direct or branched hydrocarbon group having 1 to 6 carbon atoms.
  • a thiol group an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a sec-pentyl group, and a hexyl group
  • Base and secondary hexyl particularly preferred are thiol, ethyl and isopropyl.
  • the term "d ⁇ C 6 alkoxy” refers to the above ( ⁇ ⁇ € 6 alkyl group attached to an oxygen atom of a group obtained as CH 6 alkoxy group, mention may be made Yue group, Ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, sec-pentyloxy, n-hexyloxy and hexane Oxyl; methoxy and ethoxy are particularly preferred.
  • halogen means fluorine, chlorine, bromine and iodine, and particularly preferably fluorine, chlorine and bromine.
  • the molar ratio of the metal aluminum in the cocatalyst to the central metal (ie, Fe 2+ , Co 2+ or Ni 2+ ) in the main catalyst is from 50 to less than 200 Preferably, it is 100-199.8, more preferably 148-196, and most preferably 178-196.
  • Rj Rs has the following definition:
  • the sum R 5 in the procatalyst is ethyl and both are hydrogen.
  • the method of preparing the procatalyst of the formula (I) as defined in the present invention generally comprises the steps of:
  • the alkyl-substituted aniline is preferably 2,6-diethylaniline.
  • a method for ethylene oligomerization wherein 2-aminoimido-1,10-phenanthroline iron (11), cobalt (II) of the following formula (I) is used.
  • a catalyst composition of nickel (II) as a main catalyst and triethylaluminum as a cocatalyst is from 30 to less than 200:
  • M is a central metal selected from the group consisting of Fe 2+ , Co 2+ and Ni 2+ ;
  • R R 5 are each independently selected from the group consisting of hydrogen, CH 6 alkyl, 13 ⁇ 4 , Cp ⁇ Ce alkoxy And nitro.
  • the molar ratio of the metal aluminum in the promoter to the central metal (ie, Fe 2+ , Co 2+ or Ni 2+ ) in the main catalyst is from 50 to less than 200. Preferably, it is 100-199.8, more preferably 148-196, and most preferably 178-196.
  • each of the procatalysts is independently selected from the group consisting of hydrogen, decyl, ethyl, isopropyl, fluoro, chloro, bromo, methoxy, ethoxy, and nitrate. base.
  • the sum R 5 in the main catalyst is ethyl and R 2 to R 4 are both hydrogen.
  • M and R, ⁇ R 5 in the procatalyst have the following definitions:
  • oligomerization reaction conditions involved in the above oligomerization method are well known to those skilled in the art, and the preferred technical scheme of the above oligomerization method is as follows: The organic solvent and the catalyst composition are added to the reaction vessel, and then the ethylene pressure is 0.1 ⁇ . The reaction was carried out at 30 MPa and the reaction temperature was 20 to 150 ° C for 30 to 100 minutes, and then cooled to -10 to 10 ° C, and a small amount of the reaction mixture was taken out and neutralized with 5% diluted hydrochloric acid, followed by gas chromatography (GC) analysis.
  • GC gas chromatography
  • the reaction temperature is preferably 20 to 80 ° C
  • the pressure is preferably 1 to 5 MPa
  • the reaction time is advantageously 30 to 60 minutes.
  • the organic solvent is selected from the group consisting of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, really, diphenylbenzene, and dichlorodecane, and the like.
  • the polyethylene oligomerization product obtained by the above oligomerization method includes C 4 , C 6 , C 8 , C 10 , C 12 , C 14 , C 16 , C 18 , C 20 , C 22 , etc.; ⁇ -
  • the selectivity of olefins can reach more than 95%.
  • a small amount of the reaction mixture was taken out and neutralized with 5% diluted hydrochloric acid, followed by GC analysis. The results show that the oligomerization activity can reach 10 6 g.mor 1 .!!- 1 or more, and the distribution of oligomerization products is more reasonable. Further, the remaining reaction mixture was neutralized with a 5% diluted aqueous solution of hydrochloric acid in ethanol, and no polymer was obtained.
  • triethylaluminum AlEt 3
  • AlEt 3 the monovalent amount of triethylaluminum is only a few tenths of the monovalent aluminoxane monovalent
  • the 2-imino group is chlorinated.
  • a catalyst composition of -1,10-phenanthroline iron (11), cobalt (II) or nickel (ruthenium) as a main catalyst the molar ratio of metal aluminum in the cocatalyst to the central metal in the main catalyst is 30 to In the range of less than 200, not only the catalytic activity is acceptable, but also the amount of the cocatalyst is low, which is highly practical.
  • M is a central metal, preferably selected from the group consisting of Fe 2+ , Co 2+ and Ni 2+ ; ⁇ each independently selected from hydrogen, ⁇ C 6 alkyl, halogen, d ⁇ C 6 alkoxy And nitro.
  • R ⁇ Rs in the procatalyst are each independently selected from the group consisting of hydrogen, decyl, ethyl, isopropyl, fluoro, chloro, bromo, decyloxy, ethoxy. And nitro.
  • 1 and R 5 in the main catalyst are ethyl groups and R 2 to R 4 are all hydrogen.
  • M and 1 ⁇ 1 5 in the main catalyst have the following definitions:
  • the above oligomerization method can be preferably carried out according to the following technical scheme: adding an organic solvent and a catalyst composition to the reaction vessel, and then the ethylene pressure is 0.1 to 30 MPa, and the reaction temperature is -10-19 ° C, and the reaction is 30 to 100 minutes. . Then, a small amount of the reaction mixture was taken out at -10 to 10 ° C, and neutralized with 5% diluted hydrochloric acid, followed by gas chromatography (GC) analysis.
  • GC gas chromatography
  • the main catalyst is usually used in the form of a solution
  • the solvent which can be used is a conventional solvent
  • the solvent may be selected from the group consisting of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, diphenylbenzene, dichloromethane, etc., preferably. Toluene.
  • the temperature is preferably -10 to 15 ° C, more preferably 0 to 15 ° C, and most preferably 5 to 10 ° C; the reaction time is advantageously 30 to 60 minutes; It is 1 ⁇ 5Mpa.
  • the molar ratio of the metal aluminum in the cocatalyst to the central metal in the main catalyst is 49 to 500, preferably 100 to 400, more preferably 200 to 300, and most preferably 300.
  • the organic solvent is selected from the group consisting of toluene, cyclohexane, diethyl ether, tetrahydrofuran, ethanol, benzene, xylene, and dichlorodecane, and benzene is preferred.
  • the polyethylene oligomer obtained by the above oligomerization method includes C 4 , C 6 , C 8 , C 10 , C 12 , C 14 , C 16 , C 18 , C 2 . , C 22, etc.; ⁇ -olefin selectivity can reach more than 96%; high oligomerization activity. Additionally, the remaining reaction mixture was neutralized with 5% dilute hydrochloric acid acidified ethanol solution with only a small amount of polymer produced.
  • 2-imino-1,10-phenanthroline iron (11), cobalt(II) or nickel(II) chloride as the main catalyst and low-cost triethylaluminum (AlEt 3)
  • the catalyst composition as a cocatalyst catalyzes the oligomerization of ethylene at a lower temperature (-10 ⁇ 19 °C), has a low amount of cocatalyst, and has high oligomerization activity, opening up a new ethylene oligomerization pathway.
  • the present invention adopts low cost (the monovalent amount of triethyl aluminum is only a few tenths of the unit price of fluorenyl aluminoxane) of triethyl aluminum (AlEt 3 ) as a cocatalyst, and chlorinated 2-Asia.
  • Catalyst composition based on amine-1,10-phenanthroline iron (11), cobalt (II) or nickel (II) as main catalyst, not only catalytically acceptable, high selectivity of a-olefin, but also amount of cocatalyst Low, the catalytic effect and the ⁇ are well balanced and practical.
  • the technical prejudice is overcome, the reaction conditions are optimized, and the cost of the ethylene oligomerization reaction is greatly reduced, and the comprehensive catalytic effect and the production cost have broad industrialization prospects. detailed description
  • the reactor is filled with ethylene. Maintain the ethylene pressure of IMPA and stir the reaction for 30 min.
  • the oligomerization activity is 2.02x10 6 g-mor'CFe)- ⁇ 1 , Qi
  • the content of the polymer was C 4 12.0%, C 6 - C 10 64.7%, C 6 ⁇ C 18 87.0% (including linear ⁇ -olefin 98.0%), C 20 ⁇ C 28 1.0%.
  • the analysis results are shown in Table 1.
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 2.02 ⁇ 10 6 g-mol ⁇ Fe) '!
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • Example 2 The ethylene oligomerization process described in Example 1 was repeated, in which the cocatalyst was still triethylaluminum, a solution of toluene and 0.53 ml of triethylaluminum benzene (concentration of 0.74 mol/l) and 8 ml of chlorination [2] -Acetyl-1,10-phenanthroline (2,6-diethylaniline)] Cobalt (II) (2.0 ⁇ 1) in benzene solution was added to a 300 ml stainless steel autoclave to make a total volume of 100 ml.
  • Example 10 The method of Example 1 were prepared procatalyst embodiment, except that: The absolute ethanol 5ml NiCl 2 .6H 2 0 (57.0mg, 0. 24 mmol) was added dropwise acetyl-1,10 5ml 2- A solution of phenanthroline (2,6-diethylaniline) ligand (70.6 mg, 0.2 mmol) in anhydrous ethanol was stirred at room temperature for 6 hours, and the precipitate was precipitated, filtered, washed with diethyl ether and dried to give a tan solid. It is a complex of nickel (II) chloride [2-acetyl-1,10-phenanthroline (2,6-diethylaniline)], and the yield is 96%. Elemental analysis: C 24 H 23 Cl 2 NiN 3 (483.05), test values C: 59.64; H: 4.82; N: 8.53; Theory C: 59.67; H: 4.80; N: 8.70.
  • Example 2 The ethylene oligomerization process described in Example 1 was repeated, in which the cocatalyst was still triethylaluminum, a solution of toluene and 0.53 ml of triethylaluminum benzene (concentration of 0.74 mol/l) and 8 ml of chlorination [2] -Acetyl-1,10-phenanthroline (2,6-diethylaniline)] Nickel ( ⁇ ) (2.0 ⁇ 1) in benzene solution was added to a 300ml stainless steel autoclave to make the total volume 100ml , When the temperature reached 40 ° C, the reaction vessel was charged with ethylene, maintained at an ethylene pressure of 1 MPa, and stirred for 30 minutes.
  • Example 34 of the patent CN1850339A is incorporated herein by reference, the main catalyst being chlorinated
  • the pressure of acetonitrile at 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • the cocatalyst was triethylaluminum for ethylene oligomerization.
  • Example 15 triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • the oligomerization reaction conditions are as in Example 15, except that: when the temperature of the reactor is lowered to -10 ° C, the reactor is filled with ethylene, the ethylene pressure of IMPa is maintained, the temperature is maintained at -5 ° C, and the reaction is stirred. 30min.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • the oligomerization process was as in Example 15, except that when the temperature of the reactor was lowered to -5 ° C, the reactor was charged with ethylene, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 0 ° C, and the reaction was stirred for 30 minutes.
  • the oligomerization activity was 7.92xl0 6 g-mor ⁇ Fe)- ⁇ 1 , the oligomer content is C 4 20.60%, C 6 ⁇ C 10 48.4%, C 6 ⁇ C 18 75.03% (including linear a-olefin 98.3%), C 20 ⁇ C 28 4.37%.
  • the remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to give a white waxy polymer.
  • the polymerization activity was 2.4 ⁇ 10 4
  • the results of the analysis are shown in Table 2.
  • the oligomer content are C 4 20.43 %, C 6 ⁇ C 10 45.12%, C 6 ⁇ C 18 69.81% (containing linear a-olefin 98.1%), C 20 - C 28 9.76%.
  • the remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white waxy polymer.
  • the polymerization activity was 9.6 ⁇ 10 4 g-mor ⁇ Fe)- ⁇
  • the analysis results are shown in Table 2.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • the oligomerization process was as in Example 15, except that when the temperature of the reactor was lowered to 5 ° C, the reactor was charged with ethylene, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 10 ° C, and the reaction was stirred for 30 minutes.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • the oligomerization process was as in Example 15, except that when the temperature of the reactor was lowered to 15 ° C, the reactor was charged with ethylene, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 19 ° C, and the reaction was stirred for 30 minutes.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • ethylene was charged into the reaction vessel, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes.
  • the oligomerization activity was 7.18 X 10 6
  • the oligomer content was C 4 20.24%, C 6 ⁇ C 10 46.56%, C 6 ⁇ C 18 71.52% (including linear a-olefin 98.1%), and C 2Q ⁇ C 28 8.23%.
  • the remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white waxy polymer.
  • the polymerization activity was 2.7 ⁇ 10 4 g-mol ⁇ Fe ⁇ h.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • ethylene was charged into the reaction vessel, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes.
  • the oligomerization activity was 8.96 x 10 6
  • the oligomer content is C 4 20.02%, C 6 ⁇ C 10 45.88%, C 6 ⁇ C 18 70.09% (including linear ⁇ -olefin 98.3%), C 20 ⁇ C 28 9.88%.
  • the remaining reaction mixture was 5%
  • the solution was acidified in hydrochloric acid to give a white waxy polymer.
  • the polymerization activity was 3.8 ⁇ 10 4 g-mor'CFe)- ⁇
  • the analysis results are shown in Table 2.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • ethylene was charged into the reaction vessel, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • ethylene was charged into the reaction vessel, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes.
  • the oligomerization activity was 5.81 X10 6
  • the oligomer content is C 4 21.95%, C 6 ⁇ C 10 43.78%, C 6 ⁇ C 18 68.15% (including linear ⁇ -olefin 98.8%), C 2 . ⁇ C 28 9.89%.
  • the remaining reaction mixture was neutralized with a 5% hydrochloric acid-acidified ethanol solution to obtain a white waxy polymer having a polymerization activity of 5.7 ⁇ 10 4 g-mor ⁇ Fe)- ⁇ 1 .
  • the analysis results are shown in Table 2.
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • the oligomerization process was as in Example 15, except that when the temperature of the reactor was lowered to 2 ° C, ethylene was charged into the reaction vessel, ethylene pressure of 2 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes.
  • the oligomerization activity was 11.31 X 10 6
  • the oligomer content is C 4 21.53%, C 6 ⁇ C 10 44.57%, C 6 ⁇ C 18 69.26% (including linear ⁇ -olefin 98.3%), and C 20 - C 28 9.21%.
  • Remaining reaction mixture Neutralization of 5% hydrochloric acid-acidified ethanol solution gave a white waxy polymer.
  • the polymerization activity was 9.8 ⁇ 10 4 g-mol ⁇ Fe h ⁇ .
  • triethylaluminum was used as a cocatalyst for ethylene oligomerization.
  • the oligomerization process was as in Example 15, except that when the temperature of the reactor was 2 ° C, the reactor was charged with ethylene, the ethylene pressure of 3 MPa was maintained, the temperature was maintained at 5 ° C, and the reaction was stirred for 30 minutes.
  • the ethylene oligomerization method of Example 23 was repeated except that when the temperature of the reactor reached 40 ° C, the reactor was charged with ethylene, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 40 ° C, and the reaction was stirred for 30 min. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% diluted hydrochloric acid for GC analysis: the oligomerization activity was .Uxli g'mor Fe)'!- 1 , and the oligomer content was C 4 13.1%, C, respectively.
  • the ethylene oligomerization method of Example 15 was repeated except that when the temperature of the reactor reached 40 ° C, ethylene was charged into the reaction vessel, the ethylene pressure of 1 MPa was maintained, the temperature was maintained at 40 ° C, and the reaction was stirred for 30 minutes. Thereafter, a small amount of the reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 1.93 ⁇ 10 6 g-mor ⁇ Fe)- ⁇ 1 , and the oligomer content was C 4 20.61%, respectively.
  • the main catalyst prepared in Example 1 was subjected to the ethylene oligomerization reaction as described in Example 1, without The same is true:
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • the ethylene pressure of 1 MPa was maintained at 40 ° C, and the reaction was stirred for 30 min.
  • oligomerization activity for its oligomerization activity at 40 ° C Several times to ten times, even dozens of times; even when ethylene oligomerization is carried out with methylaluminoxane as a cocatalyst, the oligomerization activity is similar at the reaction temperature (40 ° C) where the oligomerization activity is the highest.
  • reaction temperature 40 ° C
  • the method of the present invention employs a low-cost triethylaluminum which has a relatively high catalytic activity at a low temperature and has an unexpected effect.
  • reaction temperature -10 - 19 °C as the temperature increases, the oligomerization activity first increases and then decreases, and the highest value occurs at 5 °C. Table 1

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Description

乙烯齐聚催化剂组合物和齐聚方法 技术领域
本发明涉及乙烯齐聚领域， 具体涉及氯化 2-亚胺基 -1,10-菲咯啉铁（ II ) 、 钴（ II )或镍（ II )和三乙基铝的催化剂组合物。 本发明还涉及使用上述组合 物的乙烯齐聚方法。 背景技术
线性 α-烯烃在乙烯共聚单体、 表面活性剂合成中间体、 增塑剂醇、 合成润 滑油和油品添加剂等领域有着广泛的应用。 近年来， 随着聚烯烃工业的不断发 展， 世界范围内对 α-烯烃的需求量增长迅速。 目前绝大部分的 α-烯烃是由乙烯 齐聚制备得到的。 乙烯齐聚法所用的催化剂主要有镍系、 铬系、 锆系和铝系等， 近年来， Brookhart 小组 (Brookhart, M 等人， J. Am. Chem. Soc.， 1998, 120, 7143-7144; WO99/02472, 1999), Gibson小组 (Gibson, V. C.等人， Chem. Commun., 1998, 849-850; Chem. Eur. J., 2000, 2221-2231)分别发现一些 Fe(II)和 Co(II)的三 齿吡啶亚胺配合物可催化乙烯齐聚， 不但催化剂的催化活性很高， 而且 α-烯烃 的选择性也艮高。
中国科学院化学研究所的专利 CN1850339A报道了一种用于乙烯齐聚和聚 合的催化剂， 该催化剂为 2-亚胺基 -1,10-菲咯啉配位的 Fe2+、 Co2+和 Ni2+的氯化 物， 在助催化剂曱基铝氧烷作用下， 该催化剂作为主催化剂具有较好的乙烯齐 聚和聚合催化性能， 其中铁配合物对乙烯表现出很高的齐聚和聚合活性； 并且 在反应温度为 40Ό时， 齐聚活性最高； 而齐聚和聚合活性随压力的升高增加较 为明显； 齐聚产物包括 C4、 C6、 C8、 C10、 C12、 C14、 C16、 C18、 C20、 C22等； 聚 合物为低分子量聚烯烃和蜡状聚烯烃。 此专利还公开了三乙基铝为助催化剂， 氯化 [2-乙酰基 -1,10-菲咯啉 (缩 2，6-二乙基苯胺)]合铁 (Π)为主催化剂， Al/Fe比为 500、反应温度 40°C、反应时间为 lh、聚合压力 IMPa时， 齐聚活性为 2.71χ105; 此专利中还公开了以三异丁基铝和氯化二乙基铝为助催化剂时， 在高助催化剂 用量（Al/Fe比为 500 ) , 齐聚活性也较低。
从该专利的教导可见， 三乙基铝为助催化剂时， 即使在高的助催化剂用量， 齐聚活性仍然比较低， 实用性较差， 因而在其专利中主要使用高成本的曱基铝 氧烷为助催化剂。 而曱基铝氧烷成本过高， 用量过大， 作为助催化剂大规模应 用于乙烯齐聚时， 其势必导致生产成本高昂。
另外， 中国科学院化学研究所孙文华等在 Iron Complexes Bearing 2-Imino- 1 , 10-phenanthrolinyl Ligands as Highly Active Catalysts for Ethylene Oligomerization ( Organometallics 2006,25,666-677 )一文表 2中显示， 在采用氯 化 [2-乙酰基 -1,10-菲咯啉 (缩 2,6-二乙基苯胺)]合铁 (II)为主催化剂进行乙烯齐聚， 乙烯齐聚活性随温度的变化并非单调增加或者单调减小， 而是当反应温度为 20 ~ 40°C时， 齐聚活性随温度的升高而增加， 当反应温度为 4.0 ~ 60°C时， 齐聚 活性随温度的升高而降低。 这一现象在孙文华等 （ Organometallics 2007,26,2720-2734 )一文表 4采用氯化二乙基铝为助催化剂进行乙烯齐聚的实猃 结果中进一步得到证实。 发明内容
针对现有技术的缺陷， 希望寻求一种低成本实用的乙烯齐聚催化剂组合物 和齐聚方法， 以便其大规模工业应用。 经过大量的实验研究中， 惊奇的发现， 在使用少量的三乙基铝为助催化剂、氯化 2-亚胺基 -1,10-菲咯啉铁（ II )、钴（ II ) 或镍（ II ) 为主催化剂的催化剂组合物进行乙烯齐聚时， 具有可以接受的催化 活性， 这与事先认为的低活性有着显著差别。 三乙基铝的单价低、 用量少以及 可接受和适宜的催化活性， 在乙烯齐聚工艺中采用此催化剂组合物能够为大规 模工业化提供强力保障。
根据本发明的一个方面， 提供了一种乙烯齐聚催化剂组合物， 包括下式 (I) 所示的氯化 2-亚胺基 -1,10-菲咯啉铁（ II ) 、 钴（ II )或镍（ II )主催化剂和三 乙基铝助催化剂， 其中所述助催化剂中的金属铝与所述主催化剂中的中心金属 的摩尔比为 30至小于 200:
Figure imgf000004_0001
其中各变量定义如下： M为中心金属， 选自 Fe2+、 Co2+和 Ni2+; R^Rs各自 独立地选自氢、 ~C6烷基、 卤素、 d~C6烷氧基和硝基。
在本发明中，术语" Ci〜C6烷基"指的是含有 1-6个碳原子的饱和直连或支链 烃基。 作为 d~C6烷基， 可以提及曱基、 乙基、 正丙基、 异丙基、 正丁基、 异 丁基、 仲丁基、 叔丁基、 正戊基、 仲戊基、 正己基和仲己基； 特别优选曱基、 乙基和异丙基。
在本发明中，术语" d~C6烷氧基 "指的是上述 (^~€6烷基与一个氧原子连接 得到的基团。 作为 CH 6烷氧基， 可以提及曱氧基、 乙氧基、 正丙氧基、 异丙 氧基、 正丁氧基、 异丁氧基、 仲丁氧基、 叔丁氧基、 正戊氧基、 仲戊氧基、 正 己氧基和仲己氧基； 特别优选甲氧基和乙氧基。
在本发明中， 术语"卤素"指的是氟、 氯、 溴和碘， 特别优选氟、 氯和溴。 在上述催化剂组合物的优选实施方案中， 所述助催化剂中的金属铝与所述 主催化剂中的中心金属 (即 Fe2+、 Co2+或 Ni2+)的摩尔比为 50至小于 200, 优选 100-199.8, 更优选为 148~196, 最优选为 178~196。
在上述催化剂组合物的特别优选的实施方案中， 所述主催化剂中的 M和
Rj Rs具有如下定义：
1: M = Fe2+, ¾ = Me, R2 = R3 = 4 = R5 = H;
2: M = Fe2+， R2 = Me, Ri = R3 = 4 = R5 = H;
3: M = Fe2+, R3 = Me, Ri = R2 = 4 = R5 = H;
4: M = Fe2+, Rj = R2 = Me, R3 = 4 = R5 = H;
5: M = Fe2+, Rj = Me, R2 = R4 = R5 = H;
6: M = Fe2+, ¾ = R4 = Me, R2 = R3 = R5 = H;
7: M = Fe2+， ¾ = R5 = Me, R2 = R3 = R4 = H;
8: M = Fe2+， R2 = R3 = Me, Ri = R4 = R5 = H;
9: M = Fe2+, R2 = R4 = Me, Ri = R3 = R5 = H;
10: M = Fe2+, R! = R3 = R5 = Me, R2 = H;
11: M = Fe2+, Rj = Et, R2 = R3 = R4 = ¾ = H;
12: M = Fe2+, R! = Et, R5 = Me, R2 : = R3 = = R4 = H;
13: M = Fe2+, Rj = R5 = Et, R2 = R3 = H;
14: M = Fe2+, Rj = iPr, R2 = = R3 = = R5 = = H;
15: M = Fe2+, R, = R5 = iPr, R = H;
16: M = Co2+, R, = Me, R2 = R3 = R4 = R5 = H; 17: M = Co2+, R2 =Me R. =R3 = R4 =R5 =H;
Figure imgf000006_0001
20: M = Co2+, Ri = R3 = =Me R.2 = R4 =R5 =H;
Figure imgf000006_0002
23: M = Co2+, R2 = R3 = :Me Ri = R4 =R5 =H;
24: M = Co2+, R2 = R4 = Me- Ri =R3 =H;
25: M = Co2+, Ri = R3 = R5
Figure imgf000006_0003
=H;
26: M = Co2+, Ri = Et, R2 = = R4 = :R5 = :H;
27: M = Co2+, Ri = Et, R5 = Me, 2 = R4 =H;
28: M = Co2+, Ri = R5 = Et， R2 = R3 = 4 = :H;
29: M = Co2+, Ri = iPr, R2 = = R3 = = 4 : =R5 =H;
30: M = Co2+, Ri = R5 = iPr, R2 = = R3 = = 4 =H;
31: M = Ni2+, R. = Me, R2 = = : =R5 =H;
32: M = Ni2+， R2 = Me, = R3 = = R4 : =R5 =H;
33: M = Ni2+， R3 = Me, Ri: = R2 = = R4 : = 5 =H;
34: M = Ni2+, Ri = R2 = Me, R3 = = R4 : =R5 =H;
35: M = Ni2+， Ri = R3 = Me, R2 = = R4 : =R5 =H;
36: M = Ni2+, Ri = R4 = Me, R2 = = R3: =R5 =H;
37: M = Ni2+， Ri = R5 = Me, R2 = = R3 = = R4 = =H;
38: M = Ni2+, R2 = R3 = Me, Ri = = R4 = = R5 = =H;
39: M = Ni2+, R2 = = Me, = R3: =H;
40: M = Ni2+， Ri = R3 = R5 = Me, R2 = = R4 = =H;
41: M = Ni2+， R. = Et, R2 = R3 = 4 = R5 = H;
42: M = Ni2+, R. = Et, R5 = Me, 2 = = R3 = = 4 = =H;
43: M = Ni2+， Ri = R5- Et, 2 = R3 = R4 = H;
44: M = Ni2+, Ri = iPr， R2 = R R4 = R5 = =H;
45: M = Ni2+， Ri = R5 = iPr, R2 = :R3 = = R4 = =H„
在上述催化剂组合物的特别优选的实施方案中， 所述主催化剂中的 和 R5 为乙基并且 均为氢。
本发明中主催化剂的制备本身是已知的， 对此可参见 CN1850339A, 该文 献中的制备方法以引用的方式并入本文。
制备本发明限定的式 (I)主催化剂的方法通常包括如下步骤：
(1)用 2-乙酰基 -1,10-菲咯啉和取代的苯胺 (取代基选自下组： d~C6烷基、 卤素、 CH:6烷氧基和硝基)反应合成 2-亚胺基 -1，10-菲咯啉配体； 以及
(2)用步骤 1中得到的 2-亚胺基 -1,10-菲咯啉配体分别与 FeCl2.4H20、 CoCl2 或 NiCl2，6H20反应即可得到配合物。
本发明方法使用的主催化剂的具体制备过程如下：
一、 配体合成的一般方法
1 ) 2-乙酰基- 1， 10-菲咯啉和 C 烷基取代的苯胺在乙醇中以对曱苯磺酸为 催化剂回流 1 - 2天， 反应液浓缩后过碱性氧化铝柱子， 用石油醚 /乙酸乙酯 (4 : 1)淋洗， 第二馏分为产物， 除去溶剂得到黄色固体 2-亚胺基 -1,10-菲咯啉配体。
2) 2-乙酰基 -1，10-菲咯啉和氟、 C^C^烷氧基或硝基取代的苯胺以对曱苯磺 酸为催化剂并加入分子筛或无水硫酸钠作脱水剂在曱苯中回流 1 天， 过滤后除 去溶剂曱苯过碱性氧化铝柱子， 用石油醚 /乙酸乙酯 (4: 1)淋洗， 第二熘分为产 物， 除去溶剂得到黄色固体 2-亚胺基- 1， 10-菲咯啉配体。
3) 2-乙酰基-1，10-菲咯啉和氯、 溴取代的苯胺用对曱苯磺酸作催化剂， 采用 正硅酸乙酯作溶剂和脱水剂，在 140〜150°C下加热反应 1天， 减压除去正硅酸乙 酯， 然后过碱性氧化铝柱子， 用石油醚 /乙酸乙酯 (4: 1)淋洗， 第二馏分为产物， 除去溶剂得到黄色固体 2-亚胺基- 1， 10-菲咯啉配体。
所述烷基取代的苯胺优选 2，6-二乙基苯胺。
上述所有合成的 2-亚胺基 -1,10-菲咯啉配体都通过核磁、红外和元素分析得 到了证实。
二、 铁 (11)、 钴 (11)、 镍 (II)配合物合成的一般方法
将 FeCl2'4H20、 CoCl2或 NiCl2-6H20的乙醇溶液按摩尔比 1:1~1:1.2滴加到 2-亚胺基 -1,10-菲咯啉配体的溶液中， 室温搅拌， 析出沉淀， 过滤， 用***洗涤 后干燥便得到 2-亚胺基 -1，10-菲咯啉配合物。 配合物 1~45通过元素分析和红外 光谱表征得以证实。
才艮据本发明的另一方面， 提供了一种乙烯齐聚方法， 其中采用下式 (I)的氯 化 2-亚胺基 -1,10-菲咯啉铁 (11)、 钴 (II)或镍 (II)为主催化剂和三乙基铝为助催化剂 的催化剂组合物， 并且所述助催化剂中的金属铝与所述主催化剂中的中心金属 的摩尔比为 30至小于 200:
Figure imgf000008_0001
(I)
其中各变量定义如下： M为中心金属， 选自 Fe2+、 Co2+和 Ni2+; R广 R5各自 独立地选自氢、 CH 6烷基、 1¾素、 Cp^Ce烷氧基和硝基。
在上述齐聚方法的优选实施方案中， 所述助催化剂中的金属铝与所述主催 化剂中的中心金属（即 Fe2+、 Co2+或 Ni2+)的摩尔比为 50 至小于 200 , 优选 100-199.8, 更优选为 148-196, 最优选为 178~196。
在上述齐聚方法的优选的实施方案中， 所述主催化剂中的 各自独立 地选自氢、 曱基、 乙基、 异丙基、 氟、 氯、 溴、 甲氧基、 乙氧基和硝基。
在上述齐聚方法的更优选的实施方案中，所述主催化剂中的 和 R5为乙基 并且 R2~R4均为氢。
在上述齐聚方法的特别优选的实施方案中， 所述主催化剂中的 M和 R,~R5 具有如下定义：
1: M = Fe2+, R. = Me, 2 = R3 = R4 = R5 = H;
2: M = Fe2+, R2 = Me, i = R3 = R4 = R5 = H;
3: M = Fe2+, R3 = Me, Ri = R2 = R4 = R5 = H;
4: M = Fe2+, Ri = R2 = Me, R3 = 4 = R5 = H;
5: M = Fe2+, Ri = R3 = Me, R2 = 4 = R5 = H;
6: M = Fe2+, Ri = = Me, R2 = R3 = R5 = H;
7: M = Fe2+, R. = Me, R2 = R3 = 4 = H;
8: M = ■ Fce 2+ , R2 = R3 = Me, Ri = R4 = R5 = H;
9: M = Fe2+, R2 = R4 = Me, i = R3 = R5 = H;
10: M = Fe2+, Ri = R5 = Me, R2 = R4 = H;
11: M = Fe2+, Ri = Et, 2 = R3 = R4 = R5 = H;
12: M = Fe2+, Ri = Et， R5 = Me, R2 = = R3 :
13: M = Fe2+, . = R5 = Et, R2 = R3 = R4 = H; =^ = '¾Ϊ = ¾ = =ΙΜ '9
II ： εε
'Η
I II
■6Ζ
= =¾ = ιΉ =η ■2Ζ
•LZ
■Η = = 'SZ
Figure imgf000009_0001
9^ = ^ = =η 'ΛΖ
'Η = sM = ¾ = •03
■Η = =η :6ΐ
Figure imgf000009_0002
:8ΐ
■Η = 'Ή = =η •·ίΙ
Η = ¾ = =Yi -9\
■Η = =Yi
0££000/ll0ZN3/X3d 9ceozmioz OAV 上述齐聚方法涉及的齐聚反应条件对本领域熟练技术人员而言是熟知的， 上述齐聚方法优选的技术方案如下： 在反应容器中加入有机溶剂和催化剂组合 物， 然后在乙烯压力为 0.1~30MPa且反应温度为 20~150°C下反应 30-100分钟， 然后冷却至 -10〜10°C， 取出少量反应混合物用 5%的稀盐酸中和后进行气相色谱 (GC)分析。
上述齐聚方法中， 所述反应温度优选为 20 ~ 80°C， 压力优选为 l ~ 5MPa， 反应时间有利地为 30~60分钟。
上述齐聚方法中， 所述有机溶剂选自曱苯、 环己烷、 ***、 四氢呋喃、 乙 醇、 笨、 二曱苯和二氯曱烷等， 优选曱苯。
通过上述齐聚方法来齐聚乙烯， 获得的乙烯齐聚产物包括 C4、 C6、 C8、 C10、 C12、 C14、 C16、 C18、 C20、 C22等； α-烯烃的选择性可以达到 95%以上。 在乙烯 齐聚结束之后， 取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析。 结果 表明， 齐聚活性可达 106 g.mor1.!!-1以上， 齐聚产物分布更加合理。 另外， 剩余 的反应混合物用 5%的稀盐酸酸化的乙醇溶液中和， 没有得到聚合物。
通过上述齐聚方法， 采用低成本 (三乙基铝单价仅为曱基铝氧烷单价的几十 分之一)的三乙基铝 (AlEt3)为助催化剂、 氯化 2-亚胺基 -1,10-菲咯啉铁 (11)、 钴 (II) 或镍 (Π)为主催化剂的催化剂组合物， 在助催化剂中的金属铝与主催化剂中的中 心金属的摩尔比为 30至小于 200范围内， 不仅催化活性可以接受， 而且助催化 剂用量低， 具有很强的实用性。
根据本发明还提供了另外一种乙烯齐聚方法， 采用下式 (I)的氯化 2-亚胺基 -1,10-菲咯啉铁 (11)、 钴 (Π)或镍 (II)为主催化剂、 三乙基铝为助催化剂的催化剂组 合物， 乙烯齐聚反应 -10 ~ 19°C:
Figure imgf000010_0001
(I)
其中各变量定义如下： M为中心金属， 优选地选自 Fe2+、 Co2+和 Ni2+; ~ 各 自独立地选自氢、 ~C6烷基、 卤素、 d~C6烷氧基和硝基。 在上述齐聚方法的优选实施方案中， 所述主催化剂中的 R^Rs各自独立地 选自氢、 曱基、 乙基、 异丙基、 氟、 氯、 溴、 曱氧基、 乙氧基和硝基。
在上述齐聚方法的更优选的实施方案中， 所述主催化剂中的 1^和 R5为乙 基并且 R2~R4均为氢。
在上述齐聚方法的特别优选的实施方案中， 所述主催化剂中的 M和 1^~15 具有如下定义：
II
= Fe2+, R2 = Me, 11 Rj = R3 = ¾ = R5 = H;
Figure imgf000011_0001
II
4: M = Fe2+, Ri = R2 = Me, R3 = 4 = R5 = H;
5: M = Fe2+, Ri = R3 = Me, R2 = R4 = R5 = H;
6: M = Fe2+, Ri = R4 = Me, R2 = R3 = R5 = H;
7: M = Fe2+, Ri = R5 = Me, R2 = R3 = H;
8: M = Fe2+, R2 = R3 = Me, Ri = 4 = R5 = H;
9: M = Fe2+, R2 = R4 = Me, i = R3 = R5 = H;
10: M = Fe2+, Ri Me, R2 =H;
11: M = Fe2+, i = Et, R2 = R3 = R4 = R5 = H;
12: M = Fe2+, Ri = Et, R5 = Me, 2 = = R3: = R4
13: M = Fe2+, R. = R5 = Et, R2 = R3 = R4 = H;
14: M = Fe2+, Ri = iPr, R2 = = R3 = H;
15: M = Fe2+, Ri = R5 = iPr, R2 = R3 = -R4- =H;
16: M = Co2+, Ri = Me, R2 =H;
17: M = Co2+, R2 = Me, Rj
Figure imgf000011_0002
=H;
18: M = Co2+, R3 -Me, R, =R2 = 4 =R5 =H;
19: M = Co2+, Ri = R2 = Me . R3 = R4 =R5 =H;
Figure imgf000011_0003
21: M = Co2+, Ri = R4 = Me > R2 =R3 =R5 =H;
22: M
23: M
Figure imgf000011_0004
24: M = Co2+, R2 = R4 = Me > Ri =R3 =R5 =H;
25: M = Co2+, Ri = R3 = R5 = =Me = 4 =H;
26: M = Co2+, Ri = Et, R2 = :R3 = R4 = 5 = H; 27: M = Co2+, Ri = Et, R5 = Me, R2 =R3
28: M = Co2+, Ri = R5 = = Et, R2 = R3 = = :
29: M = Co2+, Ri = iPr， = R3 = =R5 =H;
30: M = Co2+, Ri = R5 = :iPr, R2 = =R3 = R4 =H;
Figure imgf000012_0001
32: M = Ni2+, R2 = Me, i: = 3 = = 4 =R5 =H;
Figure imgf000012_0002
34: M = Ni2+， Ri = R2 = Me, R3: =R5 =H;
35: M = Ni2+, Ri = R3 = Me, R2 = =R5 =H;
Figure imgf000012_0003
37: M = Ni2+, Ri = R5 = Me, R2 = =R3 = R4 =H;
Figure imgf000012_0004
39: M = Ni2+， R2 = R4 = Me, Ri = =R3 =R5 =H;
40: M = Ni2+, Ri = R3 = R5 = Me, R2 =R4 =H;
41: M - Ni2+, Ri = Et, 2 = R3 = R4 = R5 = H;
42: M = Ni2+, Ri = Et, 5 = Me, R2 =R3
43: M = Ni2+， Ri = R5 = Et, R2 = R3 = 4 = H;
44: M = Ni2+, Ri = iPr, R2 = : = =R5 =H;
45: M = Ni2+, Ri = R5 = iPr, R2 = :R3: = R4
上述齐聚方法， 可优选按如下技术方案进行： 在反应容器中加入有机溶剂 和催化剂组合物， 然后在乙烯压力为 0.1~30MPa, 并且反应温度为 -10- 19°C, 反应 30~100分钟。 然后在 -10~10°C下， 取出少量反应混合物用 5%的稀盐酸中 和后进行气相色谱 (GC)分析。
上述齐聚方法中， 主催化剂通常以溶液形式使用， 可使用的溶剂为常规溶 剂， 如溶剂可选自曱苯、 环己烷、 ***、 四氢呋喃、 乙醇、 二曱苯和二氯甲烷 等， 优选甲苯。
上述齐聚方法中， 所述温度优选 -10~15°C， 更优选 0~ 15°C， 最优选 5~ 10°C; 所述反应时间有利地为 30~60分钟； 所述反应压力优选为 1 ~5Mpa。
上述齐聚方法中， 所述助催化剂中的金属铝与所述主催化剂中的中心金属 的摩尔比为 49 ~ 500, 优选 100 ~ 400, 更优选 200 ~ 300， 最优选 300。
上述齐聚方法中， 所述有机溶剂选自曱苯、 环己烷、 ***、 四氢呋喃、 乙 醇、 苯、 二甲苯和二氯曱烷等， 优选曱苯。 通过上述齐聚方法来齐聚乙烯， 获得的乙烯齐聚产物包括 C4、 C6、 C8、 C10、 C12、 C14、 C16、 C18、 C2。、 C22等； α-烯烃的选择性可以达到 96%以上； 齐聚活 性高。 另外， 剩余的反应混合物用 5%的稀盐酸酸化的乙醇溶液中和， 只有少量 聚合物产生。
通过上述齐聚方法， 采用氯化 2-亚胺基 -1,10-菲咯啉铁 ( 11 )、 钴（II )或镍 ( II ) 为主催化剂和低成本的三乙基铝 (AlEt3)为助催化剂的催化剂组合物， 在更低温 ( -10 ~ 19°C )条件下催化乙烯齐聚， 助催化剂用量低， 齐聚活性高， 开拓了一 种新的乙烯齐聚途径。
相对于现有技术， 本发明采用低成本 (三乙基铝单价仅为曱基铝氧烷单价的 几十分之一)的三乙基铝 (AlEt3)为助催化剂、 氯化 2-亚胺基 -1,10-菲咯啉铁 ( 11 )、 钴（ II )或镍 ( II )为主催化剂的催化剂组合物， 不仅催化活性可以接受、 a-烯烃的 选择性高， 而且助催化剂用量低 ·， 催化效果和^ ^本得到较好的平衡， 实用性强。 通过本发明， 克服了技术偏见， 优化了反应条件， 且使得乙烯齐聚反应成本大 幅下降， 综合催化效果和生产成本， 工业化前景广阔。 具体实施方式
以下仅为本发明的较佳实施例而已， 不能以此限定本发明的范围。 即凡是 依本发明申请专利范围所作的变化与修饰， 皆应仍属本发明专利涵盖的范围 内。 实施例 1
一、 主催化剂的制备
2-乙酰基 -1，10-菲咯啉 (0.4445g, 2mmol)和 2,6-二乙基苯胺 (0.4175g， 2.8mmol) 加入 40mg对曱苯磺酸为催化剂并加入 2g 4A分子筛作脱水剂， 在 30ml乙醇中 回流 1 天， 过滤后除去溶剂， 剩余物用二氯曱烷溶解， 过碱性氧化铝柱子， 用 石油 乙酸乙酯 (4： 1)淋洗， 第二馏分为产物， 除去溶剂得到黄色固体， 为 2- 乙酰基 -1，10-菲咯啉 (缩 2，6-二乙基苯胺)配体， 产量为 0.6g， 产率为 84%。 核磁 分析： 'Η NMR (300 MHz, CDC13): δ 9.25 (dd, J=3.0 Hz, 1H); 8.80 (d, J=8.3 Hz, 1H); 8.35 (d， J=8.3 Hz, 1H); 8,27 (dd, J=7.8 Hz, 1H); 7.86 (s, 2H); 7.66 (m, 1H); 7.15 (d， J=7.6 Hz, 2H); 6.96 (t, J= 7.5 Hz, 1H); 2.58 (s， 3H, CH3); 2.43 (m， 4H, CH2CH3); 1.16 (t， J=7.5Hz, 6H，CH2CH3)。 元素分析： C24H23N3 (353.46)， 理论值： C: 81.55; H: 6.56; N: 11.89。 测量值： C: 80.88; H: 6.59; N: 11.78。 将 5ml FeCl2-4H20(48mg, 0.24mmol)的无水乙醇溶液滴加到 5ml 2-乙酰基 -1,10-菲咯啉 (缩 2,6-二乙基苯胺)配体 (70.6mg, 0.2mmol)的无水乙醇溶液中， 室 温搅拌 6 小时， 析出沉淀， 过滤， 用***洗涤后干燥便得到墨绿色粉末固体， 为氯化 [2-乙酰基 -1，10-菲咯啉 (缩 2，6-二乙基苯胺)]合铁 (II)配合物， 产率为 95%。 元素分析： C24H23Cl2FeN3 (480.21),测试值 C: 59.95; H: 4.92; N: 8.80; 理论 值 C: 60.03; H: 4.83; N: 8.75。
二、 乙烯齐聚反应
将曱苯和 0.53ml三乙基铝甲苯溶液 (浓度为 0.74mol/l)以及 8ml主催化剂氯 化 [2-乙酰基 -1,10-菲咯啉 (缩 2,6-二乙基苯胺)]合铁 (Π)(2.0μιηο1)的曱苯溶液加入 到 300ml的不锈钢高压釜中， 使总体积为 100ml, Al/Fe=196„ 当温度达到 40 °C 时， 往反应釜中充入乙烯， 保持 IMPa的乙烯压力， 搅拌反应 30min。 之后， 用 注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 2.02x106 g-mor'CFe)-^1 , 齐聚物含量分别为 C4 12.0%, C6 - C10 64.7%, C6 ~ C18 87.0% (其中含线性 α-烯烃 98.0%), C20 ~ C28 1.0%。 剩余的反应混合物用 5%的 盐酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 2
采用实施例 1制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与 实施例 1的不同之处在于：三乙基铝甲苯溶液的用量为 0.54ml (浓度为 0.74mol/l), 使 Al/Fe=199.8。 在 40°C下， 保持 IMPa的乙烯压力， 搅拌反应 30min。 用注射 器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析：齐聚活性为 2.02χ106 g-mol^Fe)'!!-1，齐聚物含量分别为 C4 12.1%, C6 ~ C10 64.5%, C6 ~ C18 86.8% (其 中含线性 α-烯烃 97.5%)， C2o ~ C28 l.l%。 剩余的反应混合物用 5%的盐酸酸化的 乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 3
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.51ml(浓度为 0.74mol/l)，使 Al/Fe=189。在 40°C下，保持 IMPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 1.98X 106 g-mor'CFe h-1 , 齐聚物含量分别为 C4 11.6%, C6 ~ C1064.8%, C6 ~ C18 86.9% (其中含线性 α-烯烃 98.0%), C2o ~ C28 1.5%。 剩余的反应混合物用 5%的盐 酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 4
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝甲苯溶液的用量为 0.48ml (浓度为 0.74mol/l),使 Al/Fe=178。在 40°C下，保持 IMPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 1.98X 106
Figure imgf000015_0001
齐聚物含量分别为 C4 10.5%， C6 ~ C10 65.1%, C6 ~ C18 87.7% (其中含线性 α-烯烃 98.3%), C20 ~ C28 1.8%。 剩余的反应混合物用 5%的盐 酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 5
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.4ml (浓度为 0.74mol/l),使 Al/Fe=148。在 40°C下，保持 IMPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 1.21 X 106
Figure imgf000015_0002
, 齐聚物含量分别为 C4 24.7%, C6 ~ C1057.4%, C6 ~ C18 72.7% (其中含线性 α-浠烃 92.9%), C20 ~ C282.6%。 剩余的反应混合物用 5%的盐 酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 6
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.81ml(浓度为 0.25mol/l),使 Al/Fe=101。在 40°C下，保持 IMPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 l.Ol xlO6
Figure imgf000015_0003
齐聚物含量分别为 C4 21.6%， C6 ~ C10 53.6%, C6 ~ C18 75.3% (其中含线性 α-烯烃 89.9%), C20 ~ C283.1%。 剩余的反应混合物用 5%的盐 酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 7
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.4ml (浓度为 0.25mol/l), 使 Al Fe=50。 在 40°C下， 保持 IMPa的乙烯压力， 搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 0.12x l06 g-mor^Fe)-^1 , 齐聚物含量分别为 C4 7.4%， C6 ~ C10 86.8%, C6 ~ C18 92.6% (其中含线性 α-烯烃 92.5%), C2。~ C280%。剩余的反应混合物用 5%的盐酸 酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 8
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.24ml (浓度为 0.25mol/l), 使 Al Fe=30。 在 40°C下， 保持 IMPa的乙烯压力， 搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 0.08χ106 g-mor^Fe)-^1 , 齐聚物含量分别为 C4 6.9%, C6 ~ C10 87.1%, C6 ~ C18 93.1% (其中含线性 α-婦烃 91.5%)， C2。~ C280%。剩余的反应混合物用 5%的盐酸 酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 9
采用实施例 1主催化剂的制备方法， 不同之处在于： 将 5ml CoCl2 (31.2mg， 0.24mmol)的无水乙醇溶液滴加到 5ml 2-乙酰基 -1,10-菲咯淋 (缩 2，6-二乙基苯胺） 配体 (70.6mg, 0.2mmol)的无水乙醇溶液中， 室温搅拌 6小时， 析出沉淀， 过滤， 用***洗涤后干燥便得到褐色固体，为氯化 [2-乙酰基 -1，10-菲咯啉 (缩 2,6-二乙基 苯胺)]合钴 (Π)配合物， 产率为 95%。 元素分析： C24H23Cl2CoN3(483.29)， 测试值 C: 59.69; H: 4.86; N: 8.62 ； 理论值 C: 59.64; H: 4.80; N: 8.69。
重复实施例 1 中所述的乙烯齐聚工艺， 其中助催化剂仍为三乙基铝， 将曱 苯和 0.53ml三乙基铝曱苯溶液 (浓度为 0.74mol/l)以及 8ml氯化 [2-乙酰基 -1,10- 菲咯啉 (缩 2，6-二乙基苯胺)]合钴 (II) (2.0μιηο1)的曱苯溶液加入到 300ml的不锈钢 高压釜中， 使总体积为 100ml, Al/ Co =196„ 当温度达到 40°C时， 往反应釜中 充入乙烯， 保持 IMPa的乙烯压力， 搅拌反应 30min。 之后， 用注射器取出少量 反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 1.51 χ106
Figure imgf000016_0001
, 齐聚物含量为 C4 100%。 剩余的反应混合物用 5%的盐酸酸化的 乙醇溶液中和， 没有得到聚合物。 分析结杲见表 1。 实施例 10 采用实施例 1 主催化剂的制备方法， 不同之处在于： 将 5ml NiCl2.6H20 (57.0mg, 0.24mmol)的无水乙醇溶液滴加到 5ml 2-乙酰基 -1,10-菲咯啉 (缩 2，6-二 乙基苯胺)配体 (70.6mg， 0.2mmol)的无水乙醇溶液中， 室温搅拌 6小时， 析出沉 淀， 过滤， 用***洗涤后干燥便得到黄褐色固体， 为氯化 [2-乙酰基 -1，10-菲咯啉 (缩 2,6-二乙基苯胺）]合镍（II)配合物， 产率为 96%。 元素分析： C24H23Cl2NiN3(483.05), 测试值 C: 59.64; H: 4.82; N: 8.53; 理论值 C: 59.67; H: 4.80; N: 8.70。
重复实施例 1 中所述的乙烯齐聚工艺， 其中助催化剂仍为三乙基铝， 将曱 苯和 0.53ml三乙基铝曱苯溶液 (浓度为 0.74mol/l)以及 8ml氯化 [2-乙酰基 -1,10- 菲咯啉 (缩 2，6-二乙基苯胺)]合镍 (Π)(2.0μπιο1)的曱苯溶液加入到 300ml的不锈钢 高压釜中， 使总体积为 100ml，
Figure imgf000017_0001
当温度达到 40°C时， 往反应釜中充 入乙烯， 保持 IMPa的乙烯压力， 搅拌反应 30min。 之后， 用注射器取出少量反 应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 1.40χ106
Figure imgf000017_0002
齐聚物含量为 C4 100%。 剩余的反应混合物用 5%的盐酸酸化的 乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 11
采用实施例 1制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 三 乙基铝曱苯溶液的用量为 0.53ml (浓度为 0.74mol/l)， 使 Al/Fe=196。 与实施例 1 的不同之处在于： 在 40°C下， 保持 2MPa的乙烯压力， 搅拌反应 30min。 用注 射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 3.21xl06
Figure imgf000017_0003
齐聚物含量分别为 C4 19.40%, C6 ~ C10 53.02%, C6 ~ C1875.68% (其中含线性 α-烯烃 96.9%), C20 ~ C284.92%。剩余的反应混合物用 5% 的盐酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 12
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.54ml (浓度为 0.74mol/l),使 Al/Fe= 199.8;在 40°C下，保持 2MPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 3.83X 106
Figure imgf000017_0004
齐聚物含量分别为 C421.05%， C6 ~ C1052.37%, C6 ~ C18 73.36% (其中含线性 α-烯烃 97.5%), C20 ~ C285.59%。 剩余的反应混合物用 5%的 盐酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 13
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 三乙基铝曱苯溶液的用量为 0.53ml (浓度为 0.74mol/l), 使 Al/Fe=196。 与实施例 1的不同之处在于： 在 40°C下， 保持 3MPa的乙烯压力， 搅拌反应 30min。 用注 射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 6.40xl06
Figure imgf000018_0001
齐聚物含量分别为 C4 17.5%， C6 ~ C10 46.2%, C6 ~ C18 71.5% (其中含线性 α-烯烃 98.7%), C20 ~ C28 11.0%。 剩余的反应混合物用 5%的 盐酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 实施例 14
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙浠齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 0.4ml (浓度为 0.74mol/l),使 Al/Fe=148; 在 40°C下，保持 3MPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 5.21xl06
Figure imgf000018_0002
齐聚物含量分别为 C4 19.5%， C6 ~ C10 53.4%, C6 ~ C18 75.8% (其中含线性 α-烯烃 98.4%), C20 ~ C284.7%。 剩余的反应混合物用 5%的盐 酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 对比例 1
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 1.35ml (浓度为 0.74mol/l),使 Al/Fe=500。在 40°C下，保持 IMPa的乙烯压力，搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 0.88xl06
Figure imgf000018_0003
齐聚物含量分别为 C4 37.0%, C6 ~ C10 52.0%, C6 ~ C18 63.0% (其中含线性 α-烯烃 91.5%)， C20 ~ C280%。剩余的反应混合物用 5%的盐酸 酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 对比例 2
专利 CN1850339A中实施例 34以引入的方式并入本文中， 主催化剂为氯化
[2-乙酰基 -1,10-菲咯淋 (缩 2,6-二乙基苯胺)]合铁 (II), 助催化剂为三乙基铝； 齐聚 工艺如下： 将 1000ml曱苯和 5.0ml三乙基铝 （ 1.0mol/l in hexane ) 以及 10ml主 催化剂 （ΙΟμπιοΙ ) 的曱苯溶液加入到 2000-ml不锈钢高压釜中。 机械搅拌开始， 保持 350转 /分， 当温度达到 40°C时， 往反应釜内充入乙浠， 齐聚反应开始。 在 40°C下， 保持 IMPa的乙烯压力， 搅拌反应 lh。 用注射器取出少量反应混合物 用 5%的稀盐酸中和后进行气相色谱 （GC ) 分析： 齐聚活性为 0.271 χ106
Figure imgf000019_0001
齐聚物含量分别为： C439.3%, C629.3%, C8 ~ C2231.4%。 剩余 的反应混合物用 5%的盐酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见 表 1。 对比例 3
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应， 与实施例 1 的不同之处在于： 三乙基铝曱苯溶液的用量为 2.70ml (浓度为 0.74mol/l),使 Al/Fe=1000。在 40°C下，保持 IMPa的乙烯压力，搅拌反应 30min„ 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 0.18χ106
Figure imgf000019_0002
, 齐聚物含量分别为 C4 43.9%， C6 ~ C10 50.9%, C6 ~ C18 55.5% (其中含线性 α-浠烃 84.3%)， C2o ~ C280.6%。 剩余的反应混合物用 5%的盐 酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果见表 1。 对比例 4
采用实施例 1制备的主催化剂如实施例 1所述工艺进行乙烯齐聚反应， 不 同之处在于： 助催化剂为曱基铝氧烷， 曱基铝氧烷曱苯溶液的用量为 0.26ml (浓 度为 1.5mol/l), 使 Al/Fe=195。 在 40°C下， 保持 1 MPa的乙浠压力， 搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐 聚活性为 S.SxK^ g'mor^Fe^h-1,齐聚物含量分别为 C4 14.2%, C6 ~ C10 44.9%, C6 ~ C18 74.1% (其中含线性 α-烯烃 89.0%)， C20 ~ C28 11.7%。 剩余的反应混合物 用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性为
Figure imgf000019_0003
分析结果见表 1。 从表 1可知：乙烯齐聚中采用氯化 2-亚胺基 -1,10-菲咯淋铁 (II)作为主催化剂 和三乙基铝作为助催化剂的催化剂组合物， 在较高催化剂用量（Al/Fe为 500、 1000 )时，具有低的催化活性，而在较低催化剂用量时，反而齐聚活性可达 2χ106 g-mor'-h-1 , 与相近比例下 （Al/Fe比为 195 ) 曱基铝氧烷做助催化剂时的齐聚活 性接近， 且 α-烯烃的选择性高。 这说明采用低成本的三乙基铝为助催化剂， 在 低用量下反而具有适宜的催化活性，具有预料不到的效果。并且 Al/Fe摩尔比 在 30至小于 200范围内， 随着 Al/Fe摩尔比增大， 反应活性增大； 而当 Al/ Fe摩 尔比在大于 200至 1000范围内时， 随着 Al Fe摩尔比增大，反应活性反而减小。 实施例 15
采用实施例 1 制备的主催化剂， 助催化剂为三乙基铝进行乙烯齐聚反应。 乙烯齐聚工艺如下： 将曱苯和 1.21ml(0.8954mmol)三乙基铝曱苯溶液 (浓度为 0.74mol/l)以及 12ml 氯化 [2-乙酰基 -1，10-菲咯啉（缩 2，6-二乙基苯胺)]合铁 (ΙΙ)(3.0μιηο1)的甲苯溶液加入到 300ml的不锈钢高压釜中， 使总体积为 100ml, Al/Fe=298.5。 当反应釜温度降温为 -15°C时， 往反应釜中充入乙烯， 保持 IMPa 的乙烯压力， 温度保持在 -10°C， 搅拌反应 30min。 之后， 用注射器取出少量反 应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 5.35χ106 g-mor'CFe)-^1 ,齐聚物含量分别为 C424,92%， C6 ~ C1057.03%, C6 ~ C1874.09% (其 中含线性 α-烯烃 98.1%)， C2o ~ C280.99%。 剩余的反应混合物用 5%的盐酸酸化 的乙醇溶液中和， 没有得到聚合物。 分析结果见表 2。 实施例 16
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚反应条件如实施例 15, 不同之处在于： 当反应釜温度降温为 -10°C时， 往反 应釜中充入乙烯， 保持 IMPa的乙烯压力， 温度保持在 -5°C , 搅拌反应 30min。 之后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚 活性为 JAx loG g'mor^Fe)^1 , 齐聚物含量分别为 C426.66%, C6 ~ C1048.32%, C6 ~ C1868.16% (其中含线性 α-烯烃 98.4%), C20 ~ C285.18%。 剩余的反应混合物 用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 9.2χ103
Figure imgf000020_0001
分析结果见表 2。 实施例 17
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15 , 不同之处在于： 当反应釜温度降温为 -5°C时， 往反应釜 中充入乙烯， 保持 IMPa的乙烯压力， 温度保持在 0°C， 搅拌反应 30min。 之后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 7.92xl06 g-mor^Fe)-^1 , 齐聚物含量分别为 C4 20.60%, C6 ~ C10 48.4%, C6 ~ C1875.03% (其中含线性 a-烯烃 98.3%), C20 ~ C284.37%。剩余的反应混合物用 5% 的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 2.4χ 104
Figure imgf000021_0001
分析结果见表 2。 实施例 18
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15, 不同之处在于： 当反应釜温度降温为 2°C时， 往反应釜 中充入乙烯， 保持 IMPa的乙烯压力， 温度保持在 5°C， 搅拌反应 30min。 之后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 10.24x l06 g-mor^Fe)-!!-1 , 齐聚物含量分别为 C420.43%, C6 ~ C1045.12%, C6 ~ C18 69.81% (其中含线性 α-烯烃 98.1%), C20 - C28 9.76%。 剩余的反应混合物用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 9.6χ104 g-mor^Fe)-^^ 分析结果见表 2。 实施例 19
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15, 不同之处在于： 当反应釜温度降温为 5°C时， 往反应釜 中充入乙烯， 保持 IMPa的乙烯压力， 温度保持在 10°C , 搅拌反应 30min。 之 后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活 性为 9.35xl06 g-mol'^Fe)-^1 , 齐聚物含量分别为 C4 19.50%， C6 ~ C10 44.13%, C6 ~ C18 69.52% (其中含线性 α-烯烃 98.3%), C2。 ~ C28 10.98%。 剩余的反应混合 物用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 6.8χ104
Figure imgf000021_0002
分析结果见表 2。 实施例 20
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15, 不同之处在于： 当反应釜温度降温为 10°C时， 往反应釜 中充入乙烯， 保持 IMPa的乙烯压力， 温度保持在 15°C , 搅拌反应 30min。 之 后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活 性为 6.88xl06 g-mor'CFe)-!!-1 , 齐聚物含量分别为 C4 20.23%, C6 ~ C,0 49.23%, C6 ~ C1872.75% (其中含线性 α-烯烃 97.7%), C20 ~ C287.02%。 剩余的反应混合物 用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 2.1 xl04 g-mor^Fe)'!^ 分析结果见表 2。 实施例 21
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15， 不同之处在于： 当反应釜温度降温为 15°C时， 往反应釜 中充入乙烯， 保持 IMPa的乙烯压力， 温度保持在 19°C , 搅拌反应 30min。 之 后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活 性为 5.53xl06 g-mol^CFe)-^1 , 齐聚物含量分别为 C4 20.60%, C6 ~ C10 48.49%, C6 ~ C1872.21% (其中含线性 α-烯烃 98.2%)， C2Q ~ C287.19%。 剩余的反应混合物 用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 1.4χ104
Figure imgf000022_0001
分析结果见表 2。 实施例 22
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15 , 不同之处在于： 三乙基铝曱苯溶液的用量为 1.62ml(1.1988mmol), Al/Fe=399.6。 当反应釜温度降温为 0°C时， 往反应釜中充 入乙烯， 保持 IMPa的乙烯压力， 温度保持在 5°C， 搅拌反应 30min。 之后， 用 注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 7.18X 106
Figure imgf000022_0002
齐聚物含量分别为 C4 20.24%, C6 ~ C10 46.56%, C6 ~ C1871.52% (其中含线性 α-烯烃 98.1%), C2Q ~ C288.23%。剩余的反应混合物用 5% 的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 2.7χ104 g-mol^Fe^h 分析结果见表 2。 实施例 23
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15， 不同之处在于： 三乙基铝曱苯溶液的用量为 0.81ml(0.5994mmol), Al/Fe=199,8。 当反应釜温度降温为 0°C时， 往反应釜中充 入乙烯， 保持 IMPa的乙烯压力， 温度保持在 5 °C , 搅拌反应 30min。 之后， 用 注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 8.96x106
Figure imgf000022_0003
, 齐聚物含量分别为 C4 20.02%， C6 ~ C10 45.88%, C6 ~ C1870.09% (其中含线性 α-烯烃 98.3%), C20 ~ C289.88%。剩余的反应混合物用 5% 的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 3.8xl04 g-mor'CFe)-^^ 分析结果见表 2。 实施例 24
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15 , 不同之处在于： 三乙基铝曱苯溶液的用量为 0.40ml(0.296mmol), Al/Fe=98.7。 当反应釜温度降温为 0°C时， 往反应釜中充入 乙烯， 保持 IMPa的乙烯压力， 温度保持在 5°C , 搅拌反应 30min。 之后， 用注 射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 8.26x106
Figure imgf000023_0001
, 齐聚物含量分别为 C4 23.56%， C6 ~ C10 47.31%, C6 ~ C1869.32% (其中含线性 α-烯烃 98.5%)， C20 ~ C287.12%。 剩余的反应混合物用 5% 的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 7.8χ104 g-mor^Fe).!!- 分析结果见表 2。 实施例 25
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙稀齐聚反应。 齐聚工艺如实施例 15 , 不同之处在于： 三乙基铝曱苯溶液的用量为 0.20ml(0.148mmol) ， Al/Fe=49.3。 当反应釜温度降温为 0°C时， 往反应釜中充入 乙烯， 保持 IMPa的乙烯压力， 温度保持在 5°C， 搅拌反应 30min。 之后， 用注 射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 5.81 X106
Figure imgf000023_0002
, 齐聚物含量分别为 C4 21.95%, C6 ~ C10 43.78%, C6 ~ C1868.15% (其中含线性 α-烯烃 98.8%)， C2。 ~ C289.89%。剩余的反应混合物用 5% 的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 5.7χ 104 g-mor^Fe)-^1., 分析结果见表 2。 实施例 26
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15, 不同之处在于： 当反应釜温度降温为 2°C时， 往反应釜 中充入乙烯， 保持 2MPa的乙烯压力， 温度保持在 5°C， 搅拌反应 30min。 之后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐聚活性为 11.31 X 106
Figure imgf000023_0003
, 齐聚物含量分别为 C421.53%， C6 ~ C1044.57%, C6 ~ C18 69.26% (其中含线性 α-烯烃 98.3%)， C20 - C28 9.21%。 剩余的反应混合物用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 9.8xl04 g-mol^Fe h^ 分析结果见表 2。 实施例 27
采用实施例 1 制备的主催化剂， 三乙基铝为助催化剂进行乙烯齐聚反应。 齐聚工艺如实施例 15, 不同之处在于： 当反应釜温度为 2°C时， 往反应釜中充 入乙烯， 保持 3MPa的乙烯压力， 温度保持在 5 °C , 搅拌反应 30min。 之后， 用 注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 13.54xl06 g-mor'CFe)-^1, 齐聚物含量分别为 C422.12%， C6 ~ Ci044.43%, C6 ~ C18 69.12% (其中含线性 α-烯烃 98.2%), C20 ~ C28 8.76%。 剩余的反应混合物用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 Ι.ΟχΙΟ5
Figure imgf000024_0001
分析结果见表 2。 对比例 5
重复实施例 23的乙烯齐聚方法，不同之处在于：当反应釜温度达到 40°C时， 往反应釜中充入乙烯， 保持 IMPa 的乙烯压力， 温度保持在 40 °C , 搅拌反应 30min„ 之后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分 析： 齐聚活性为 .Uxli g'mor Fe)'!!-1, 齐聚物含量分别为 C4 13.1%, C6 ~ C10 64.0%, C6 ~ C18 82.8% (其中含线性 α-烯烃 98.2%), C20 ~ C28 4.1%。 剩余的反 应混合物用 5%的盐酸酸化的乙醇溶液中和， 没有得到聚合物。分析结果见表 2。 对比例 6
重复实施例 15的乙烯齐聚方法，不同之处在于：当反应釜温度达到 40°C时， 往反应釜中充入乙烯， 保持 IMPa 的乙烯压力， 温度保持在 40°C， 搅拌反应 30min。 之后， 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分 析： 齐聚活性为 1.93X 106 g-mor^Fe)-^1, 齐聚物含量分别为 C4 20.61%, C6 ~ Cio 55.17%, C6 ~ C18 75.37% (其中含线性 α-烯烃 97.0%), C20 ~ C28 4.02%。 剩 余的反应混合物用 5%的盐酸酸化的乙醇溶液中和， 没有得到聚合物。 分析结果 见表 2。 对比例 7
采用实施例 1制备的主催化剂如实施例 1所述工艺进行乙烯齐聚反应， 不 同之处在于： 助催化剂为曱基铝氧烷， 曱基铝氧烷曱苯溶液的用量为 0.54ml (浓 度为 1.5mol/l)， 使 Al/Fe=400。 在 40°C下， 保持 1 MPa的乙烯压力， 搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC分析： 齐 聚活性为 l.OSxli^ g'mor Fe).!!-1，齐聚物含量分别为 C4 16.4%, C6 ~ C10 45.2%, C6 ~ C18 73.0% (其中含线性 α-烯烃 95.0%), C20 ~ C28 10.6%。 剩余的反应混合物 用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性为
Figure imgf000025_0001
分析结果见表 2。 对比例 8
采用实施例 1制备的主催化剂如实施例 1所述工艺进行乙烯齐聚反应， 不 同之处在于： 助催化剂为甲基铝氧烷， 曱基铝氧烷曱苯溶液的用量为 1.36ml (浓 度为 1.5mol/l的曱苯溶液)，使 Al/Fe=1000。在 40°C下，保持 IMPa的乙烯压力， 搅拌反应 30min。 用注射器取出少量反应混合物用 5%的稀盐酸中和后进行 GC 分析： 齐聚活性为 l^l xK^ g'mor^Fe)'!!-1, 齐聚物含量分别为 C4 35.0%, C6 ~ C10 40.4%, C6 ~ C18 64.7% (其中含线性 α-烯烃 99.3%)， C20 ~ C28 0.3%。 剩余的 反应混合物用 5%的盐酸酸化的乙醇溶液中和， 得到白色蜡状聚合物， 聚合活性 为
Figure imgf000025_0002
分析结果见表 2。 从表 2可知： 乙烯齐聚中采用氯化 2-亚胺基 -1，10-菲咯啉铁 (Π)作为主催化剂 和三乙基铝作为助催化剂的催化剂组合物， 在较低反应温度（-10 ~ 19°C )催化 下， 具有较高的催化活性， 齐聚活性可达 107 g.mor1.!!-1以上， 齐聚活性为其在 40°C下齐聚活性的几倍到十几倍， 甚至数十倍； 甚至与甲基铝氧烷做助催化剂 进行乙烯齐聚时， 齐聚活性最高的反应温度下 （40°C ) 时的齐聚活性相近。 这 就证实本发明的方法， 采用低成本的三乙基铝， 在低温下反而具有较高的催化 活性， 具有预料不到的效果。 并且在反应温度 -10 - 19°C范围内， 随着温度的增 大， 齐聚活性先增大后减小， 最高值出现在 5°C时。 表 1
Figure imgf000026_0001
表 2
Figure imgf000027_0001

Claims

权利要求书
1. 一种乙烯齐聚催化剂组合物，包括下式 (I)所示的氯化 2-亚胺基 -1,10-菲咯 啉铁（ II ) 、 钴（ II )或镍（ II )主催化剂和三乙基铝助催化剂， 所述助催化 剂中的金属铝与所述主 至小于 200:
Figure imgf000028_0001
其中各变量定义如下： M为中心金属， 选为 Fe2+、 Co2+和 Ni2+; 各自独立 地选自氢、 d~C6烷基、 卤素、 CH^烷氧基和硝基。
2.根据权利要求 1的组合物， 其特征在于， 所述助催化剂中的金属铝与所 述主催化剂中的中心金属的摩尔比为 50至小于 200。
3.根据权利要求 1的组合物， 其特征在于， 所述助催化剂中的金属铝与所 述主催化剂中的中心金属的摩尔比为 100〜199.8。
4.根据权利要求 1的组合物， 其特征在于， 所述助催化剂中的金属铝与所 述主催化剂中的中心金属的摩尔比为 148~196。
5.根据权利要求 1的组合物， 其特征在于， 所述助催化剂中的金属铝与所 述主催化剂中的中心金属的摩尔比 178~196。
6.根据权利要求 1的组合物， 其特征在于， 主催化剂中的 ~R5各自独立 地选自氢、 曱基、 乙基、 异丙基、 氟、 氯、 溴、 曱氧基、 乙氧基和硝基。
7.根据权利要求 1的组合物， 其特征在于， 主催化剂中的 和 为乙基， R2~R4均为氢。
8.根据权利要求 1的组合物， 其特征在于， 主催化剂中的 M和 RHR5具有 如下定义：
1: M = Fe2+， R, = Me, R2 = R3 = R4 = R5 = H;
2: M = Fe2+, R2 = Me, R, = R3 = R4 = R5 = H;
3: M = Fe2+, R3 = Me, = R2 = R4 = R5 = H; 4: M = Fe2+, i = : R2 = Me, R3 = R4 = R5 = H;
5: M = Fe2+, Ri = R3 = Me, R2 = R4- H;
6: M = Fe2+， R.= R4 = Me, R2 = R3 = = H;
7: M = = Fe2+, Ri = R5 = Me, R2 = R3 = H;
8: M = = Fe2+, R2 = R3 = Me, Ri = 5 = H;
9: M = = Fe2+, R2 = R4 = Me, Ri = R3 = R5 = H;
Figure imgf000029_0001
: M = Fe2+, Ri = Et, R2 = R3 = R4 = R5 = H;
12: M = Fe2+， Ri = Et, R5 = Me, R2 = =R3 =R4
13: M = Fe2+， R. = R5 = Et, R2 = R3 = R4 = H;
14: M = Fe2+, Ri = iPr, R2 = : R3 = R4 = = R5: =H;
15: M = Fe2+, Ri = R5 = iPr, R2 = R3 = =H;
16: M = Co2+, Ri = Me， R2 =R3 =R4 =R5 =H;
17: M = Co2+, R2 = Me, R, =R3 = 4 =R5 =H;
18: M = Co2+, R3 = Me, R, =R2 = R4 =R5 =H;
19: M = Co2+, Ri = R2 = Me, R3 = 4 = 5 =H;
20: M = Co2+, Ri = R3 = Me, R2 -R4 =R5 =H;
21: M = Co2+, Ri = R4 = Me, R2 =R3 =R5 =H;
22: M = Co2+, Ri =R5 = Me, R2 =H;
23: M
Figure imgf000029_0002
=H;
24: M = Co2+, R2 = R4 = Me, Ri =R3 =R5 =H;
25: M = Co+, Ri = R3 = R5 = Me, R2 = 4 =H;
26: M = Co2+, . = Et, R2 = R3 = R5 = H;
27: M = Co2+, Ri = Et, R5 = Me, R2 =R3 = R4
28: M = Co2+, Ri = R5 = Et, R2 = R3 = 4 = H;
29: M = Co2+, Ri = iPr, R2 = = R3: = : = R5: =H;
30: M = Co2+, Ri = R5 = iPr, R =R = 4: =H;
31: M = Ni2+， Ri = Me, R2 = ： R3: = R4 = = R5: =H;
32: M = Ni2+, R2 = Me, Rj = = R4 = = R5 = =H;
33: M = Ni2+， R3 = Me, R = R2 = = R4: = R5 = =H;
34: M = Ni2+， Ri = R2 = Me, R3 = =¾: -R5 =H;
35: M = Ni2+, Ri =R3 = Me, 2 = = R5 = =H; 36: M = Ni2十, i Me, R2 =R3 =R5 =H;
37: M = Ni2+， Ri = R5 = Me, R2 = R4 =H;
38: M = Ni2+， R2 = R3 = Me, . = R4 =R5 =H;
39: M = Ni2+, R2 = R4 = Me, R. =R3 =R5 =H;
40: M = Ni2+, i = R3 = R5 = Me, R2 = R4 =H;
41: M = Ni2+， Ri = Et, R2 = R3 = R4 = R5 = =H;
42: M = Ni2+, Ri = Et, 5 = Me, 2 =R3 = R4
43: M = Ni2+， Ri = R5 = Et, R2 = R3 = R4 = H;
44: M = Ni2+， Ri = iPr, R2 = R3 = = 5 =H;
45: M = Ni2+, Ri = R5 = iPr, R2 = ： R3 = = R4 = =H。
9. 一种乙烯齐聚方法， 其特征在于， 采用下式 (I)的氯化 2-亚胺基 -1,10-菲咯 啉铁（ II ) 、 钴（ II )或镍（ II )作为主催化剂和三乙基铝作为助催化剂的催 化剂组合物， 所述助催化剂中的金属铝与所述主催化剂中的中心金属的摩尔比 为 30至小于 200:
Figure imgf000030_0001
其中各变量定义如下： M为中心金属， 选自 Fe2+、 Co2+和 Ni2+; 〜 各自独立 地选自氢、 C,~C6烷基、 素、 C,~C6烷氧基和硝基。
10.根据权利要求 9的组合物， 其特征在于， 所述助催化剂中的金属铝与所 述主催化剂中的中心金属的摩尔比为 50至小于 200.
11.根据权利要求 9的方法， 其特征在于， 所述助催化剂中的金属铝与所述 主催化剂中的中心金属的摩尔比为 100~199.8。
12. 根据权利要求 9的方法， 其特征在于， 所述助催化剂中的金属铝与所述 主催化剂中的中心金属的摩尔比为 148〜196。
13.根据权利要求 9的方法， 其特征在于， 所述助催化剂中的金属铝与所述 主催化剂中的中心金属的摩尔比 178〜196。
14.根据权利要求 9的方法， 其特征在于， 主催化剂中的 R,~R5各自独立地 选自氢、 曱基、 乙基、 异丙基、 氟、 氯、 溴、 甲氧基、 乙氧基和硝基。
15. 根据权利要求 9的方法， 其特征在于， 主催化剂中的 和 为乙基， R2~R4均为氢。
16.才艮据权利要求 9的方法， 其特征在于， 主催化剂中的 M和 R^Rs具有 如下定义：
1: M = Fe2+, Ri = Me, R2 = R3 = R4 = R5 = H;
2: M = Fe2+, R2 = Me, Ri = R3 = = R5 = H;
3: M = Fe2+, R3 = Me, Ri = R2 = R5 = H;
4: M = Fe2+, Ri = R2 = Me, R3 = 4 = R5 = H;
5: M = Fe2+, Ri = R3 = Me, R2 = 4 = R5 = H;
6: M = Fe2+, Ri = 4 = Me, R2 = R3 = R5 = H;
7: M = Fe2+, Ri = R5 = Me, R2 = R3 = H;
Figure imgf000031_0001
9: M = Fe2+, R2 = R4 = Me, Ri = R3 = R5 = H;
10: M = Fe 2+ , Ri =R3 = R5 = Me, R2 = R4 =H;
11: M = Fe2+, Ri = Et, R2 = R3 = R4 = R5 = H;
12: M = Fe2+, Ri = Et， 5 = Me, R2 = ： R3: = R4 = H;
13: M = Fe , Rj = R5 = Et, R2 = 3 = R4 = H;
14: M = Fe2+, R! = iPr, R2 = R3 = R4 = R5 = H;
15: M = Fe2+, Ri = R5 = iPr, R2 = R3 = -R4- =H;
Figure imgf000031_0002
19: M = Co2+, Ri = R2 = Me, R3 = =R4 =R5 =H;
Figure imgf000031_0003
21: M = Co2+, Ri = R4 = Me, R2 = =R3 =R5 =H;
Figure imgf000031_0004
23: M = Co2+, R2 = R3 = Me, Ri = =R5 =H;
24: M = Co2+, R2 = 4 = Me, R =R5 =H;
25: M = Co2+, Ri
Figure imgf000031_0005
=H;
26: M = Co2+, Ri = Et, R2 = R3 = :H;
27: M = Co2+, Ri = Et, R5 = Me, R2 =R3 =R4 28: M = Co'+, Ri = R5 = :Et, R2: = R3: = 4: =H;
29: M = Co2+, Ri = iPr, R2 -R4 =R5 =H;
30: M = Co2+, R. = R5 = :iPr, R2 =R3 = R4 =H;
31: M = Ni2+, Ri = Me， R2 =R3 -R4 =R5 =H;
Figure imgf000032_0001
33: M = Ni2+， R3 = Me, R
Figure imgf000032_0002
=H;
34: M = Ni2+， Ri = R2 = Me, R3 = 4 = 5 =H;
35: M = Ni2+, Ri = R3 = Me, R2 = 4 = 5 =H;
40: M = Ni2+, Ri = R3 = R5
41: M = Ni2+, Ri = Et, R2
42: M = Ni2+, R. = Et, R5
Figure imgf000032_0004
43: M = Ni2+， Ri = R5 = Et, R2 = = H;
44: M = Ni2+, Ri = iPr, R2 = R3 = = R4 = = R5 = =H;
45: M = Ni2+, Ri = R5 = iPr, R2 = = R3: =H。
17.根据权利要求 9中的方法，其特征在于，乙烯齐聚反应温度为 20~80°C。
18.根据权利要求 9中的方法，其特征在于，乙烯齐聚反应压力为 1 ~5MPa。
19. 一种乙烯齐聚方法， 其特征在于， 采用下式 (I)的氯化 2-亚胺基 -1，10-菲 咯啉铁 ( II ) 、 钴（ II )或镍（ II )作为主催化剂和三乙基铝作为助催化剂的 催化剂组合物， 乙烯 -10- 19°C:
Figure imgf000032_0005
〜 各自独立 地选自氢、 （^~( 6烷基、 卤素、 d Ce烷氧基和硝基。
20.根据权利要求 19所述的方法，其特征在于，齐聚反应温度为 -10~ 15°C。
21.根据权利要求 19所述的方法， 其特征在于， 齐聚反应温度为 0~ 15° (：。
22.根据权利要求 19所述的方法， 其特征在于， 齐聚反应温度为 5~10°C。
23.根据权利要求 19所述的方法， 其特征在于， 主催化剂中的 RHR5各自 独立地选自氢、 曱基、 乙基、 异丙基、 氟、 氯、 溴、 曱氧基、 乙氧基和硝基。
24.根据权利要求 19所述的方法， 其特征在于， 主催化剂中的 1 ,和115为 乙基、 R2~R4均为氢。
25. 根据权利要求 19所述的方法， 其特征在于， 主催化剂中的 M和 Rp^Rs 具有如下定义：
1: M = Fe2+, Ri = Me, R2 = 3 = 4 = R5 = H;
2: M = Fe2+, R2 = Me, Ri = R3 = R4 = R5 = H;
3: M = Fe2+, R3 = Me, Ri = R2 = = R5 = H;
4: M = Fe2+, Ri = R2 = Me, R3 = 4 = R5 = H;
5: M = Fe2+, Ri = R3 = Me, R2 = 4 = R5 = H;
6: M = Fe2+, i = R4 = Me, R2 = R3 = R5 = H;
7: M = Fe2+, Ri = 5 = Me, R2 = R3 = H;
8: M = Fe2+, R2 = R3 = Me, Ri = R5 = H;
9: M = Fe2+, R2 = R4 = Me, Ri = R3 = H;
10: M = Fe2+, Ri = R3 = R5 = Me, R2 =H;
11: M = Fe2+, R. = Et, R2 = R3- 5 = H;
12: M = Fe2+, R】 = Et, R5 = Me, = R3 = = R4 = H;
13: M = Fe2+, Ri = R5 = Et, R2 = R3 = R4 = H;
14: M = Fe2+, Ri = iPr, R2 = = R3: = R4 = =H;
15: M = Fe2+， Ri = R5 = iPr， 2 = = R3 = =H;
Figure imgf000033_0001
19: M = Co2+ ， Ri = R2 = Me ， R3 = R4 = 5 =H;
20: M
Figure imgf000033_0002
=H;
21: M = Co2+ ， Ri = R4 = Me , R2 =R3 =R5 =H;
22: M =H; 23: M = Co2+, R2 = R3 = Me, Ri = 4 =R5 =H;
24: M = Co2+, R2 = RA = Me, Ri =R3 =R5 =H;
25: M -- Co2+, Ri = R3 = R5 = Me, R2 = R4 =H;
26: M = Co2+, . = Et， 2 = R3 = = R5 = =H;
27: M ― Co2+, Ri = Et, R5 = Me, 2 = 3 = R4
28: M = Co2+, Ri = R5 = Et, R2 = R3 = = R4 = =H;
29: M = Co+, Ri = iPr, R =R5 =H;
30: M Co2+, Ri = R5 = iPr, R2: =R3 =H;
31: M = Ni2+， Ri = Me, : :R3 = =R5 =H;
32: M = Ni2+, R2 = Me, i = = R3: =R5 =H;
33: M = Ni2+, R3 = Me, i = = R2 = =R5 =H;
Figure imgf000034_0001
35: M = Ni2+, Ri = R3 = Me, R = R4 =R5 =H;
36: M = Ni2+, Ri = R4 = Me, R2: =H;
37: M = Ni2+， Ri = R5 = Me, R =R3 = R4 =H;
38: M = Ni2+, R2 = 3 = Me, R = 5 =H;
Figure imgf000034_0002
40: M = Ni2+, Ri = R3 = R5 = Me, = R4 =H;
41: M = Ni2+, Ri = Et, R2 = R3- R5 = H;
42: M = Ni2+, Ri = Et， R5 = Me, R2 = 3 = R4
43: M ：二 Ni2+， Ri = R5 = Et, R2 = R3 = 4 = H;
44: M = Ni2+, Ri = iPr, R2 = R3 = R4 : = R5 = =H;
45: M = Ni2+， Ri = R5 = iPr, R2 = R3: = R4 : =H;
26.根据权利要求 19所述的方法， 其特征在于， 所述助催化剂中金属铝与 所述主催化剂中的中心金属的摩尔比为 49 ~ 500。
27.根据权利要求 19所述的方法， 其特征在于， 所述助催化剂中金属铝与 所述主催化剂中的中心金属的摩尔比为 100 ~ 400。
28.根据权利要求 19所述的方法， 其特征在于， 所述助催化剂中金属铝与 所述主催化剂中的中心金属的摩尔比为 200 ~ 300。
29.根据权利要求 19所述的方法， 其特征在于， 所述助催化剂中金属铝与 所述主催化剂中的中心金属的摩尔比为 300。
30.根据权利要求 19-29中的任何一项所述的方法， 其特征在于， 其中乙 烯齐聚反应压力为 0.1~30MPa。
31.根据权利要求 19~29中的任何一项所述的方法， 其特征在于， 其中乙 烯齐聚反应压力为 1 ~5MPa。
32.根据权利要求 19-29中的任何一项所述的方法， 其特征在于， 所述乙 烯齐聚用有机溶剂选自曱苯、 环己烷、 ***、 四氢呋喃、 乙醇、 苯、 二甲苯和 二氯曱烷.
33.根据权利要求 19-29中的任何一项所述的方法， 其特征在于， 所述乙 烯齐聚用有机溶剂为曱苯。
PCT/CN2011/000550 2010-03-31 2011-03-30 乙烯齐聚催化剂组合物和齐聚方法 WO2011120336A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2986717A1 (fr) * 2012-02-10 2013-08-16 IFP Energies Nouvelles Composition catalytique et procede d'oligomerisation des olefines utilisant ladite composition catalytique

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA201402828B (en) * 2013-04-17 2014-12-23 China Petroleum & Chem Corp Catalyst compositions and process for ethylene oligomerization
FR3039430B1 (fr) * 2015-07-29 2019-07-05 IFP Energies Nouvelles Nouvelle composition catalytique a base de nickel et de ligand de type phosphine et son utilisation dans un procede d'oligomerisation des olefines
WO2017024188A1 (en) 2015-08-05 2017-02-09 Alibaba Group Holding Limited Method and apparatus for service authentication cross-reference to related applications
US10407360B2 (en) * 2017-12-22 2019-09-10 Chevron Phillips Chemical Company Lp Ethylene oligomerization processes
AR124323A1 (es) * 2020-12-15 2023-03-15 Shell Int Research UN PROCESO PARA PRODUCIR a-OLEFINAS
CN115555049A (zh) * 2022-09-22 2023-01-03 中化泉州石化有限公司 一种用于乙烯三聚的催化剂组合物及其应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1850339A (zh) * 2005-04-22 2006-10-25 中国科学院化学研究所 一种用于乙烯齐聚和聚合的催化剂及制备方法和用途

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2104088C1 (ru) * 1993-02-03 1998-02-10 Филлипс Петролеум Компани Способ получения каталитической системы для тримеризации, олигомеризации или полимеризации олефинов (варианты) и способ тримеризации, олигомеризации или полимеризации олефинов с использованием полученной каталитической системы
JP2000202299A (ja) * 1999-01-20 2000-07-25 Tosoh Corp エチレンの三量化触媒及びこれを用いたエチレンの三量化方法
JP4674023B2 (ja) * 1999-09-02 2011-04-20 出光興産株式会社 遷移金属化合物、α−オレフィン製造用触媒及びα−オレフィンの製造方法
WO2007105657A1 (ja) * 2006-03-10 2007-09-20 Kyoto University クロスカップリング反応を用いたオリゴマー化合物の合成方法
US20100267910A1 (en) * 2007-12-21 2010-10-21 Basell Polyolefine Gmbh Catalyst system for olefin polymerization comprising phenanthroline-comprising iron complexes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1850339A (zh) * 2005-04-22 2006-10-25 中国科学院化学研究所 一种用于乙烯齐聚和聚合的催化剂及制备方法和用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIE, SUYUN ET AL.: "Iron (II) Complexes Ligated by 2-Imino-1, 10-Phenanthrolines: Preparation and Catalytic Behavior toward Ethylene Oligomerization", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 269, 18 May 2007 (2007-05-18), pages 90 - 93 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2986717A1 (fr) * 2012-02-10 2013-08-16 IFP Energies Nouvelles Composition catalytique et procede d'oligomerisation des olefines utilisant ladite composition catalytique
US9050590B2 (en) 2012-02-10 2015-06-09 IFP Energies Nouvelles Catalytic composition and process for oligomerization of olefins using said catalytic composition

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